Method for producing fluorine-containing acrylate

ABSTRACT

A process for producing a fluorine-containing acrylic acid ester represented by CH 2 ═C(Rf)(COOR) characterized in that 1-bromo-1-perfluoroalkylethene represented by CH 2 ═CBr—Rf, or 1,2-dibromo-1-perfluoroalkylethane represented by CH 2 CBr—CHBr—Rf is allowed to react with an alcohol represented by ROH in the presence of a palladium catalyst, carbon monoxide, and two or more kinds of bases. The fluorine-containing acrylic acid ester is a useful compound having wide applications in materials for pharmaceuticals and functional polymers.

TECHNICAL FIELD

The present invention relates to a process for producing afluorine-containing acrylic acid ester which is a useful compound widelyused as materials and the like for pharmaceuticals and functionalpolymers.

BACKGROUND ART

Conventionally, the following methods have been known for producing afluorine-containing acrylic acid ester.

-   (1) A method in which α-(trifluoromethyl)acrylic acid is allowed to    react with thionyl chloride to render it α-(trifluoromethyl)acrylyl    chloride, which is then reacted with a fluorine-containing alcohol    in the presence of a base to generate α-(trifluoromethyl)acrylic    acid ester (Patent document 1).-   (2) A method in which α-(trifluoromethyl)acrylic acid is allowed to    react with a fluorine-containing alcohol or methanol in the presence    of fuming sulfuric acid to generate α-(trifluoromethyl)acrylic acid    ester (Patent document 2).-   (3) A method in which 2-bromo-3,3,3-trifluoropropene is allowed to    react with ethanol in the presence of palladium catalyst, carbon    monoxide, and triethylamine single base (Patent document 3).

However, the method (1) has such a drawback that the yield of convertingreaction into α-(trifluoromethyl)acrylyl chloride is low, and ananhydride is generated as a byproduct. The method (2) has such adrawback that use of a great amount of hard-to-handle fuming sulfuricacid is necessary. The method (3) has such a drawback that alkoxyfluorine-containing propionic acid ester is produced as a main product.In this patent document, we can find the description“1,1,1-trifluoro-2,3-dihalopropane may be used while directly convertedinto 2-halo-3,3,3-trifluoropropene within the system” but not apractical example for reaction with alcohol. Also, the fact thatreaction in the presence of two or more kinds of bases will improve theyield of fluorine-containing acrylic acid ester has never been known(see Comparative examples).

(Patent document 1) Japanese Examined Patent Publication No. Hei 3-8329

(Patent document 2) Japanese Patent Laid-Open Publication No. Sho60-42352

(Patent document 3) Japanese Patent Laid-Open Publication No. Sho58-154529

DISCLOSURE OF THE INVENTION

It is an object of the present invention to provide a process forproducing a fluorine-containing acrylic acid ester by which manydrawbacks accompanying the conventional arts as described above areovercome, and which realizes simplicity and high versatility.

The inventors of the present application diligently searched forsolution for the drawbacks accompanying the conventional approaches asdescribed above, and found a simple, versatile and highly selectiveprocess for producing a fluorine-containing acrylic acid ester using1-bromo-1-perfluoroalkylethene or 1,2-dibromo-1-perfluoroalkylethane asa starting material, and finally accomplished the present invention.

Specifically, the present invention provides a process for producing afluorine-containing acrylic acid ester represented by the generalformula (IV):

(wherein, Rf represents a perfluoroalkyl group and R represents anunsubstituted or substituted alkyl group),wherein 1-bromo-1-perfluoroalkylethene represented by the generalformula (I):

(wherein Rf is as defined above), or1,2-dibromo-1-perfluoroalkylethane represented by the general formula(II):

(wherein Rf is as defined above) is allowed to react with an alcoholrepresented by the general formula (III):ROH  (III)(wherein R is as defined above) in the presence of a palladium catalyst,carbon monoxide, and two or more kinds of bases.

BEST MODE FOR CARRYING OUT THE INVENTION

The “alkyl group” used in the present invention refers to a straight,branched, or cyclic alkyl group having 1 to 20, preferably 1 to 15carbon(s) optionally having a substituent not involved in the reaction.Examples of such alkyl groups include methyl group, ethyl group, propylgroup, isopropyl group, butyl group, t-butyl group, 1-methylpropylgroup, 2-methylpropyl group, pentyl group, 1,1-dimethylpropyl group,1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-methylbutyl group,2-methylbutyl group, 3-methylbutyl group, cyclopropyl group, cyclobutylgroup, 1-methylpentyl group, dimethylcyclopropyl group, methylcyclobutylgroup, cyclopentyl group, hexyl group, cyclohexyl group,3-methylcyclohexyl group, 4-1-methylpentyl group, methylcyclohexylgroup, heptyl group, octyl group, cyclohexylmethyl group,1-cyclohexylethyl group, cyclooctyl group, 3-hydroxy-1-adamantyl group,1,3-adamantanediyl group, nonyl group, decyl group, 1-menthyl group,1-adamantyl group, 2-adamantyl group, 2-methyl-2-adamantyl group,2-ethyl-2-adamantyl group, 2-propyl-2-adamantyl group,2-butyl-2-adamantyl group, norbornyl group, bicyclo[2,2,2]octyl group,bicyclo[3,2,1]octyl group, 2,2,2-trifluoroethyl group,4,4,4-trifluorobutyl group, 2-methoxyethyl group, and benzyl group.

The “perfluoroalkyl group” used in the present invention refers to astraight, branched, or cyclic fluorinated alkyl group having 1 to 20,preferably 1 to 10 carbon(s). Examples of such fluorinated alkyl groupsinclude trifluoromethyl group, perfluoroethyl group, perfluoropropylgroup, perfluoro isopropyl group, perfluorobutyl group,perfluoro-sec-butyl group, perfluoro-tert-butyl group, perfluoroisopentyl group, perfluorohexyl group, perfluoro octyl group, perfluorodecyl group, and the like, with perfluoro alkyl groups having 1 to 4carbon(s) being preferred, and trifluoromethyl group being morepreferred.

The present invention is conducted in the presence of a palladiumcatalyst. Examples of the palladium catalyst that can be used includemetal palladiums such as palladium black and palladium sponge; supportedpalladium such as palladium/carbon, palladium/alumina,palladium/asbestos, palladium/barium sulfate, palladium/bariumcarbonate, palladium/calcium carbonate, and palladium/polyethyleneamine; palladium salts such as palladium chloride, palladium bromide,palladium iodide, palladium acetate, palladium trifluoroacetate,palladium nitrate, palladium oxide, palladium sulfate, palladiumcyanate, allyl palladium chloride dimmer, and palladium acetyl acetate;palladium complex salts and complex compounds such as sodium hexachloropalladate, potassium hexachloro palladate, sodium tetrachloro palladate,potassium tetrachloro palladate, potassium tetrabromo palladate,tetra(acetonitrile)palladium fluoroborate, ammonium tetrachloropalladate, ammonium hexachloro palladate, dichlorobis(acetonitrile)palladium, dichloro bis(benzonitrile)palladium, andtris(dibenzylidene acetone)dipalladium; amine-based complexes such asdichlorodiamine palladium, palladium tetraamine nitrate, tetraaminepalladium tetrachloro palladate, dichlorodipyridine palladium,dichloro(2,2′-bipyridyl)palladium,dichloro(4,4′-dimethyl-2,2′-bipyridyl)palladium,dichloro(phenanthroline)palladium, (phenanthroline)palladium nitrate,dichloro(tetramethyl phenanthroline)palladium, (tetramethylphenanthroline)palladium nitrate, diphenanthroline palladium nitrate,and bis(tetramethyl phenanthroline) palladium nitrate; phosphine-basedcomplexes such as dichloro bis(triphenylphosphine)palladium, dichlorobis(tricyclohexylphosphine)palladium, tetrakis(triphenylphosphine)palladium,dichloro[1,2-bis(diphenylphosphino)ethane]palladium,dichloro[1,3-bis(diphenylphosphino)propane]palladium,dichloro[1,4-bis(diphenylphosphino)butane]palladium, anddichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium.

In the cases of amine-based complexes or phosphine-based complexes, theymay be prepared in a reaction system by adding a ligand to a precursorpalladium compound. Examples of the ligand for the amine-based complexesthat can be used for preparation in a system include ammonia,diethylamine, triethylamine, 1,2-bis(dimethylamino)ethane,1,2-bis(diphenyamino)ethane, 1,2-bis(dimethylamino)propane,1,3-bis(dimethylamino)propane, pyridine, aminopyridine,dimethylaminopyridine, 2,2′-bipyridyl, 4,4′-dimethyl-2,2′-bipyridyl,2,2′-biquinoline, phenanthroline, tetramethyl phenanthroline, and thelike.

Examples of the ligand for phosphine-based complex that can be used forpreparation in a system include triphenylphosphine,tricyclohexylphosphine, tri-t-butylphosphine,1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane,1,4-bis(diphenylphosphino)butane, 1,1′-bis(diphenylphosphino)ferrocene,sodium diphenylphosphinobenzene-3-sulfonate, tricyclohexylphosphine,tri(2-furyl)phosphine, tris(2,6-dimethoxyphenyl)phosphine,tris(4-methoxyphenyl)phosphine, tris(4-methylphenyl)phosphine,tris(3-methylphenyl)phosphine, tris(2-methylphenyl)phosphine, and thelike.

These palladium catalysts may be used in a so-called catalytic amount,which is selected in the range of about 0.0001 to 0.1 equivalent,usually in the range of about 0.001 to 0.05 equivalent, relative to1-bromo-1-perfluoroalkyllethene represented by the general formula (I)or 1,2-dibromo-1-perfluoroalkylethane represented by the general formula(II).

The alcohol represented by the general formula (III) is a straight,branched, or cyclic aliphatic alcohol having 1 to 20 carbon(s),optionally having a substituent not involved in the reaction. Examplesof the alcohol include methanol, ethanol , propanol, butanol, pentanol,hexanol, octanol, cyclohexylethanol, 2-propanol, 2-methyl-2-propanol,2-butanol, 2-hexanol, 2-methyl-1-propanol, cyclopentanol, cyclohexanol,cyclooctanol, 3-methylcyclohexanol, 4-methylcyclohexanol, cyclohexylmethanol, benzylalcohol, 2,2,2-trifluoroethanol,ethyleneglycolmonomethylether, 1-menthol, 1-adamantanol,2-methyl-2-adamantanol, 2-ethyl-2-adamantanol, 2-butyl-2-adamantanol,1,3-adamantanediol, and 2-norbornanol. Such an alcohol may be used in anamount which is equivalent or large excess to1,2-dibromo-1-perfluoroalkylethane represented by the general formula(I), and the alcohol may also serve as a solvent. Usually, it may beused in an amount ranging from 1 to 5 equivalent(s).

In the process of the present invention, the reaction is conducted underthe pressure of carbon monoxide. The reaction method is not particularlylimited, and it may be carried out in a batch or semi-batch manner. Thecarbon monoxide pressure is usually selected from the range of 0.1 to 10MPaG, however, about 0.5 to 5 MPaG is preferable in respect of reactionefficiency from the view points of safety and economy.

The present invention is conducted in the presence of two or more kindsof bases, and preferably, at least one kind from these two or more kindsof bases is an inorganic base, an inorganic salt or an organometalliccompound, and preferably, at least one kind of base is amines.

Examples of the inorganic salt that can be used include alkaline metalalkoxides such as sodium methoxide, sodium ethoxide, sodium t-butoxide,potassium methoxide, potassium ethoxide, and potassium t-butoxide;alkaline earth metal alkoxides such as magnesium diethoxide andmagnesium dimethoxide; and anion exchange resins.

Examples of the inorganic salt that can be used include alkaline metalhydrides such as lithium hydride, sodium hydride and potassium hydride;alkaline earth metal hydrides such as beryllium hydride, magnesiumhydride, and calcium hydride; alkaline metal hydroxides such as lithiumhydroxide, sodium hydroxide, and potassium hydroxide; alkaline earthmetal hydroxides such as beryllium hydroxide, magnesium hydroxide, andcalcium hydroxide; alkaline metal carbonates such as lithium carbonate,sodium carbonate, and potassium carbonate; and alkaline earth metalcarbonates such as beryllium carbonate, magnesium carbonate, and calciumcarbonate.

Examples of the organometallic compound that can be used include organicalkaline metal compounds such as butyl lithium, t-butyl lithium, phenyllithium, triphenylmethyl sodium, and ethyl sodium; and organic alkalineearth metal compounds such as methylmagnesium bromide,dimethylmagnesium, phenylmagnesium chloride, phenylcalcium bromide, andbis(dicyclobentadiene)calcium.

Examples of the amines that can be used include tertiary amines such astrimethylamine, triethylamine, tributylamine, N,N-dimethylaniline,dimethylbenzylamine, and N,N,N′,N′-tetramethyl-1,8-naphthalenediamine;and heteroaromatic amines such as pyridine, pyrrole, uracil, collidine,and lutidine.

In respect of two or more kinds of bases used in the present invention,bases combining an inorganic base, an inorganic salt, or anorganometallic compound with amines are preferred from the view pointsof reaction yield efficiency, and selectivity.

The inorganic base, the inorganic salt, or the organometallic compoundis preferably used in such an amount that at least one kind has a molarratio of 0.001 to 1, relative to the compound represented by the generalformula (I) or (II) from the view point of yield, reaction efficiencyand selectivity.

The use amount of amines may be selected in the range of from molarratio of 1 to large excess to the compound represented by the generalformula (I) or (II), and usually about 1 to 8 equivalent(s).

In practicing the present invention, the alcohol represented by thegeneral formula (III) may serves also as a solvent, and it is preferredto use a solvent that is inert to reactions. Examples of the solventthat can be used include aromatic solvents such as benzene, toluene, andxylene; hydrocarbon solvents such as hexane and octane; and polarsolvents such as acetone, acetonitrile, acetone, sulfolane,tetrahydrofuran, dioxane, dimethoxyethane, diglyme, dimethylsulfoxide,N,N-dimethylformamide, N,N-dimethylacetoamide, N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone, and hexamethyl phosphoryl triamide. Theuse amount of the solvent is not particularly limited insofar as a partor a whole of materials is dissolved at a reaction temperature.

The reaction temperature may be appropriately selected in the range offrom room temperature to 300° C., however, the range from 50° C. to 160°C. is preferred from the view point of reaction efficiency.

EXAMPLES

In the following, the present invention will be described in more detailby way of examples and comparative examples, however the presentinvention is not limited by these examples.

Example 1

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), ethanol (0.057 g, 1.24 mmol), triethylamine (0.202 g, 2.0mmol), 60%-sodium hydride (0.0080 g, 0.2 mmol),dichlorobis(triphenylphosphine) palladium (II) (0.0070 g, 0.01 mmol),and tetrahydrofuran (2.0 mL), which were then stirred at 100° C. for 15hours after introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F-NMR integration value revealed that 2-trifluoromethylacrylic acid ethyl ester was obtained with a yield of 74.9% on the basisof 2,3-dibromo-1,1,1-trifluoropropane standard. Also 5.1% of3-ethoxy-2-(trifluoromethyl)propionic acid ethyl ester was obtained.

2-trifluoromethyl acrylic acid ethyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −65.9 (t, J=1.50 Hz)

GC-MS MS (EI): m/z 169 (M⁺+1), 123 (100%)

3-ethoxy-2-(trifluoromethyl)propionic acid ethyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −66.8 (d, J=8.52 Hz)

Comparative Example 1

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), ethanol (0.057 g, 1.24 mmol), triethylamine (0.223 g, 2.2mmol), dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01mmol), and tetrahydrofuran (2.0 mL), which were then stirred at 100° C.for 15 hours after introducing carbon monoxide (1.0 MPaG). After the endof the reaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid ethyl ester was obtained with a yield of 64.6% on the basisof 2,3-dibromo-1,1,1-trifluoropropane. Also 13.2% of3-ethoxy-2-(trifluoromethyl)propionic acid ethyl ester

Example 2

An autoclave was charged with 2,3-dibrom-6-1,1,1-trifluoropropane(0.2559 g, 1.0 mmol), ethanol (0.057 g, 1.24 mmol), triethylamine (0.202g, 2.0 mmol), sodium carbonate (0.0106 g, 0.1 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtetrahydrofuran (2.0 mL), which were then stirred at 100° C. for 5 hoursafter introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid ethyl ester was obtained with a yield of 81.6% on the basisof 2,3-dibromo-1,1,1-trifluoropropane. Also, 3.0% of3-ethoxy-2-(trifluoromethyl)propionic acid ethyl ester was obtained.

Example 3

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), ethanol (0.057 g, 1.24 mmol), triethylamine (0.202 g, 2.0mmol), lithium carbonate (0.0074 g, 0.1 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtetrahydrofuran (2.0 mL), which were then stirred at 100° C. for 5 hoursafter introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid ethyl ester was obtained with a yield of 84.7% on the basisof 2,3-dibromo-1,1,1-trifluoropropane. Also 2.8% of3-ethoxy-2-(trifluoromethyl)propionic acid ethyl ester was obtained.

Example 4

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 1-propanol (0.072 g, 1.2 mmol), triethylamine (0.202 g,2.0 mmol), sodium carbonate (0.0106 g, 0.1 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtetrahydrofuran (2.0 mL), which were then stirred at 100° C. for 15hours after introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid propyl ester was obtained with a yield of 80.2% on thebasis of 2,3-dibromo-1,1,1-trifluoropropane. Also, 3.8% of3-propoxy-2-(trifluoromethyl)propionic acid propyl ester was obtained.

2-trifluoromethyl acrylic acid propyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −65.8 (t, J=1.52 Hz)

GC-MS MS (CI): m/z 183 (M⁺+1)

3-propoxy-2-(trifluoromethyl)propionic acid propyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −66.7 (d, J=8.53 Hz)

Comparative Example 2

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 1-propanol (0.072 g, 1.2 mmol), triethylamine (0.223 g,2.2 mmol), dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01mmol), and tetrahydrofuran (2.0 mL), which were then stirred at 120° C.for 5 hours after introducing carbon monoxide (1.0 MPaG). After the endof the reaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid propyl ester was obtained with a yield of 65.4% on thebasis of 2,3-dibromo-1,1,1-trifluoropropane. Also 8.9% of3-propoxy-2-(trifluoromethyl)propionic acid propyl ester was obtained.

Example 5

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 1-butanol (0.089 g, 1.2 mmol), triethylamine (0.202 g, 2.0mmol), sodium carbonate (0.0106 g, 0.1 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtetrahydrofuran (2.0 mL), which were then stirred at 100° C. for 15hours after introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid butyl ester was obtained with a yield of 82.6% on the basisof 2,3-dibromo-1,1,1-trifluoropropane. Also 3.5% of3-butoxy-2-(trifluoromethyl)propionic acid butyl ester was obtained.

2-trifluoromethyl acrylic acid butyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −65.7 (t, J=1.48 Hz)

GC-MS MS (CI): m/z 197 (M⁺+1)

3-butoxy-2-(trifluoromethyl)propionic acid butyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −66.7 (d, J=8.53 Hz)

Comparative Example 3

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 1-butanol (0.089 g, 1.2 mmol), triethylamine (0.223 g, 2.2mmol), dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01mmol), and tetrahydrofuran (2.0 mL), which were stirred at 120° C. for 5hours after introducing carbon monoxide (1.0 MPaG) After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid butyl ester was obtained with a yield of 68.7% on the basisof 2,3-dibromo-1,1,1-trifluoropropane. Also 9.3% of3-butoxy-2-(trifluoromethyl)propionic acid butyl ester was obtained.

Example 6

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 2-methyl-1-propanol (0.089 g, 1.2 mmol), triethylamine(0.202 g, 2.0 mmol), sodium carbonate (0.0106 g, 0.1 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtoluene (2.0 mL), which were then stirred at 100° C. for 15 hours afterintroducing carbon monoxide (1.0 MPaG). After the end of the reaction,the autoclave was cooled, ventilated, and added with benzotrifluoride asan internal standard substance, followed by stirring and leaving stillfor a while to let a salt precipitate. Quantification using a ¹⁹F—NMRintegration value revealed that 2-trifluoromethyl acrylic acid2-methyl-1-propyl ester was obtained with a yield of 82.0% on the basisof 2,3-dibromo-1,1,1-trifluoropropane. Also 3.1% of3-(2-methyl-1-propyloxy)-2-(trifluoromethyl)propionic acid2-methyl-1-propyl ester was obtained.

2-trifluoromethyl acrylic acid 2-methyl-1-propyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −65.8 (t, J=1.48 Hz)

GC-MS MS (CI): m/z 197 (M⁺+1)

3-(2-methyl-1-propyloxy)-2-(trifluoromethyl)propionic acid2-methyl-1-propyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −66.7 (d, J=8.52 Hz)

Comparative Example 4

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 2-methyl-1-propanol (0.089 g, 1.2 mmol), triethylamine(0.223 g, 2.2 mmol), dichlorobis(triphenylphosphine)palladium(II)(0.0070 g, 0.01 mmol), and toluene (2.0 mL), which were stirred at 120°C. for 5 hours after introducing carbon monoxide (1.0 MPaG). After theend of the reaction, the autoclave was cooled, ventilated, and addedwith benzotrifluoride as an internal standard substance, followed bystirring and leaving still for a while to let a salt precipitate.Quantification using a ¹⁹F—NMR integration value revealed that2-trifluoromethyl acrylic acid 2-methyl-1-propyl ester was obtained witha yield of 65.1% on the basis of 2,3-dibromo-1,1,1-trifluoropropane.Also 9.2% of 3-(2-methyl-1-propyloxy)-2-(trifluoromethyl)propionic acid2-methyl-1-propyl ester was obtained.

Example 7

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 1-pentanol (0.106 g, 1.2 mmol), triethylamine (0.202 g,2.0 mmol), sodium carbonate (0.0106 g, 0.1 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtoluene (2.0 mL), which were then stirred at 100° C. for 15 hours afterintroducing carbon monoxide (1.0 MPaG). After the end of the reaction,the autoclave was cooled, ventilated, and added with benzotrifluoride asan internal standard substance, followed by stirring and leaving stillfor a while to let a salt precipitate. Quantification using a ¹⁹F—NMRintegration value revealed that 2-trifluoromethyl acrylic acid pentylester was obtained with a yield of 84.0% on the basis of2,3-dibromo-1,1,1-trifluoropropane. Also 4.5% of3-pentyloxy-2-(trifluoromethyl)propionic acid pentyl ester was obtained.

2-trifluoromethyl acrylic acid pentyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −65.7 (t, J=1.51 Hz)

GC-MS MS (CI): m/z 211 (M⁺+1)

3-pentyloxy-2-(trifluoromethyl)propionic acid pentyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −66.8 (d, J=8.45 Hz

Comparative Example 5

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 1-pentanol (0.106 g, 1.2 mmol), triethylamine (0.223 g,2.2 mmol), dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01mmol), and toluene (2.0 mL), which were stirred at 120° C. for 5 hoursafter introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid pentyl ester was obtained with a yield of 72.3% on thebasis of 2,3-dibromo-1,1,1-trifluoropropane. Also 11.0% of3-pentyloxy-2-(trifluoromethyl)propionic acid pentyl ester was obtained.

Example 8

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), cyclohexyl methanol (0.137 g, 1.2 mmol), triethylamine(0.202 g, 2.0 mmol), sodium carbonate (0.0106 g, 0.1 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtetrahydrofuran (2.0 mL), which were stirred at 120° C. for 5 hoursafter introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid cyclohexylmethyl ester was obtained with a yield of 80.7%on the basis of 2,3-dibromo-1,1,1-trifluoropropane. Also 4.4% of3-cyclohexylmethyloxy-2-(trifluoromethyl)propionic acid cyclohexylmethylester was obtained.

2-trifluoromethyl acrylic acid cyclohexylmethyl ester

¹⁹F-NMR (250 MHz, CDCl₃, δ ppm): −65.7 (t, J=1.46 Hz)

GC-MS MS (CI): m/z 237 (M⁺+1)

3-cyclohexylmethyloxy-2-(trifluoromethyl)propionic acid cyclohexylmethylester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −66.7 (d, J=8.54 Hz)

Comparative Example 6

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), cyclohexyl methanol (0.137 g, 1.2 mmol), triethylamine(0.223 g, 2.2 mmol), dichlorobis(triphenylphosphine)palladium(II)(0.0070 g, 0.01 mmol) and tetrahydrofuran (2.0 mL), which were stirredat 120° C. for 5 hours after introducing carbon monoxide (1.0 MPaG)After the end of the reaction, the autoclave was cooled, ventilated, andadded with benzotrifluoride as an internal standard substance, followedby stirring and leaving still for a while to let a salt precipitate.Quantification using a ¹⁹F—NMR integration value revealed that2-trifluoromethyl acrylic acid cyclohexylmethyl ester was obtained witha yield of 66.9% on the basis of 2,3-dibromo-1,1,1-trifluoropropane.Also 11.3% of 3-cyclohexylmethyloxy-2-(trifluoromethyl)propionic acidcyclohexylmethyl ester was obtained.

Example 9

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), benzyl alcohol (0.130 g, 1.2 mmol), triethylamine (0.202g, 2.0 mmol), lithium carbonate (0.0148 g, 0.2 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtetrahydrofuran (2.0 mL), which were stirred at 120° C. for 5 hoursafter introducing carbon monoxide (1.0 MPaG) After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid benzyl ester was obtained with a yield of 71.7% on thebasis of 2,3-dibromo-1,1,1-trifluoropropane. Also 7.8% of3-benzyloxy-2-(trifluoromethyl)propionic acid benzyl ester was obtained.

2-trifluoromethyl acrylic acid benzyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −65.8 (t, J=1.34 Hz)

GC-MS MS (CI): m/z 231 (M⁺+1)

3-benzyloxy-2-(trifluoromethyl)propionic acid benzyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −66.5 (d, J=8.36 Hz)

Comparative Example 7

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), benzyl alcohol (0.119 g, 1.1 mmol), triethylamine (0.223g, 2.2 mmol), dichlorobis(triphenylphosphine)palladium(II) (0.0070 g,0.01 mmol) and tetrahydrofuran (2.0 mL), which were then stirred at 120°C. for 15 hours after introducing carbon monoxide (1.0 MPaG). After theend of the reaction, the autoclave was cooled, ventilated, and addedwith benzotrifluoride as an internal standard substance, followed bystirring and leaving still for a while to let a salt precipitate.Quantification using a ¹⁹F—NMR integration value revealed that2-trifluoromethyl acrylic acid benzyl ester was obtained with a yield of48.2% on the basis of 2,3-dibromo-1,1,1-trifluoropropane. Also 4.5% of3-benzyloxy-2-(trifluoromethyl)propionic acid benzyl ester was obtained.

Example 10

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 2-methoxyethanol (0.091 g, 1.2 mmol), triethylamine (0.202g, 2.0 mmol), sodium carbonate (0.0106 g, 0.1 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtoluene (2.0 mL), which were stirred at 120° C. for 5 hours afterintroducing carbon monoxide (1.0 MPaG). After the end of the reaction,the autoclave was cooled, ventilated, and added with benzotrifluoride asan internal standard substance, followed by stirring and leaving stillfor a while to let a salt precipitate. Quantification using a ¹⁹F—NMRintegration value revealed that 2-trifluoromethyl acrylic acid2-methoxyethyl ester was obtained with a yield of 74.8% on the basis of2,3-dibromo-1,1,1-trifluoropropane. Also 4.8% of3-(2-methoxyethyloxy)-2-(trifluoromethyl)propionic acid 2-methoxyethylester was obtained.

2-trifluoromethyl acrylic acid 2-methoxyethyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −65.9 (t, J=1.44 Hz)

GC-MS MS (CI): m/z 199 (M⁺+1)

3-(2-methoxyethyloxy)-²-(trifluoromethyl)propionic acid 2-methoxyethylester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −66.7 (d, J=8.45 Hz)

Comparative Example 8

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 2-methoxyethanol (0.091 g, 1.2 mmol), triethylamine (0.223g, 2.2 mmol), dichlorobis(triphenylphosphine)palladium(II) (0.0070 g,0.01 mmol), and toluene (2.0 mL), which were stirred at 120° C. for 5hours after introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid 2-methoxyethyl ester was obtained with a yield of 68.6% onthe basis of 2,3-dibromo-1,1,1-trifluoropropane. Also 9.9% of3-(2-methoxyethyloxy)-2-(trifluoromethyl)propionic acid 2-methoxyethylester was obtained.

Example 11

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 2-propanol (0.072 g, 1.2 mmol), triethylamine (0.202 g,2.0 mmol), 60%-sodium hydride (0.0080 g, 0.2 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol) andtoluene (2.0 mL), which were stirred at 120° C. for 5 hours afterintroducing carbon monoxide (1.0 MPaG). After the end of the reaction,the autoclave was cooled, ventilated, and added with benzotrifluoride asan internal standard substance, followed by stirring and leaving stillfor a while to let a salt precipitate. Quantification using a ¹⁹F—NMRintegration value revealed that 2-trifluoromethyl acrylic acid 2-propylester was obtained with a yield of 70.9% on the basis of2,3-dibromo-1,1,1-trifluoropropane. Also 1.2% of3-(2-propyloxy)-2-(trifluoromethyl)propionic acid 2-propyl ester wasobtained.

2-trifluoromethyl acrylic acid 2-propyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −65.9 (t, J=1.48 Hz)

GC-MS MS (EI): m/z 167 (M⁺-Me, 13), 123 (100%)

MS(CI): m/z 183 (M⁺+1)

3-(2-propyloxy)-2-(trifluoromethyl)propionic acid 2-propyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −66.8 (d, J=8.52 Hz)

Comparative Example 9

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 2-propanol (0.072 g, 1.2 mmol), triethylamine (0.223 g,2.2 mmol), dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01mmol) and tetrahydrofuran (2.0 mL), which were stirred at 120° C. for 5hours after introducing carbon monoxide (1.0 MPaG) After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid 2-propyl ester was obtained with a yield of 53.1% on thebasis of 2,3-dibromo-1,1,1-trifluoropropane. Also 3.7% of3-(2-propyloxy)-2-(trifluoromethyl)propionic acid 2-propyl ester wasobtained.

Example 12

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 2-propanol (0.072 g, 1.2 mmol), triethylamine (0.202 g,2.0 mmol), sodium carbonate (0.0106 g, 0.1 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtetrahydrofuran (2.0 mL), which were then stirred at 100° C. for 5 hoursafter introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid 2-propyl ester was obtained with a yield of 83.0% on thebasis of 2,3-dibromo-1,1,1-trifluoropropane. Also 0.8% of3-(2-propyloxy)-2-(trifluoromethyl)propionic acid 2-propyl ester wasobtained.

Example 13

An autoclave was charged with 2,3-dibromo-1,1,1trifluoropropane (0.2559g, 1.0 mmol), 2-hexanol (0.123 g, 1.2 mmol), triethylamine (0.202 g, 2.0mmol), sodium carbonate (0.0106 g, 0.1 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtetrahydrofuran (2.0 mL), which were then stirred at 100° C. for 15hours after introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid 1-methylpentyl ester was obtained with a yield of 84.0% onthe basis of 2,3-dibromo-1,1,1-trifluoropropane. Also 0.9% of3-(1-methylpentyloxy)-2-(trifluoromethyl)propionic acid 1-methylpentylester was obtained.

2-trifluoromethyl acrylic acid 1-methylpentyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −65.8 (t, J=1.41 Hz)

GC-MS MS (CI): m/z 225 (M⁺+1)

3-(1-methylpentyloxy)-2-(trifluoromethyl)propionic acid 1-methylpentylester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −66.72 (d, J=8.52 Hz), −66.74 (d,J=8.61 Hz), −66.78 (d, J=8.65 Hz), −66.79 (d, J=8.59 Hz)

Comparative Example 10

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 2-hexanol (0.123 g, 1.2 mmol), triethylamine (0.223 g, 2.2mmol), dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01mmol), and tetrahydrofuran (2.0 mL), which were stirred at 120° C. for 5hours after introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid 1-methylpentyl ester was obtained with a yield of 72.9% onthe basis of 2,3-dibromo-1,1,1-trifluoropropane. Also 4.8% of3-(1-methylpentyloxy)-2-(trifluoromethyl)propionic acid 1-methylpentylester was obtained.

Example 14

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), cyclohexanol (0.120 g, 1.2 mmol), triethylamine (0.202 g,2.0 mmol), sodium carbonate (0.0106 g, 0.1 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtoluene (2.0 mL), which were then stirred at 100° C. for 15 hours afterintroducing carbon monoxide (1.0 MPaG). After the end of the reaction,the autoclave was cooled, ventilated, and added with benzotrifluoride asan internal standard substance, followed by stirring and leaving stillfor a while to let a salt precipitate. Quantification using a ¹⁹F—NMRintegration value revealed that 2-trifluoromethyl acrylic acidcyclohexyl ester was obtained with a yield of 80.5% on the basis of2,3-dibromo-1,1,1-trifluoropropane. Also 1.2% of3-cyclohexyloxy-2-(trifluoromethyl)propionic acid cyclohexyl ester wasobtained.

2-trifluoromethyl acrylic acid cyclohexyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −65.8 (t, J=1.48 Hz)

GC-MS MS (CI): m/z 223 (M⁺+1)

3-cyclohexyloxy-2-(trifluoromethyl)propionic acid cyclohexyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −66.8 (d, J=8.52 Hz)

Comparative Example 11

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), cyclohexanol (0.120 g, 1.2 mmol), triethylamine (0.223 g,2.2 mmol), dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01mmol), and toluene (2.0 mL), which were stirred at 120° C. for 5 hoursafter introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid cyclohexyl ester was obtained with a yield of 73.4% on thebasis of 2,3-dibromo-1,1,1-trifluoropropane. Also 5.3% of3-cyclohexyloxy-2-(trifluoromethyl)propionic acid cyclohexyl ester wasobtained.

Example 15

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), cyclooctanol (0.154 g, 1.2 mmol), triethylamine (0.202 g,2.0 mmol), sodium carbonate (0.0106 g, 0.1 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtoluene (2.0 mL), which were then stirred at 100° C. for 15 hours afterintroducing carbon monoxide (1.0 MPaG). After the end of the reaction,the autoclave was cooled, ventilated, and added with benzotrifluoride asan internal standard substance, followed by stirring and leaving stillfor a while to let a salt to precipitate. Quantification using a ¹⁹F—NMRintegration value revealed that 2-trifluoromethyl acrylic acidcyclooctyl ester was obtained with a yield of 83.7% on the basis of2,3-dibromo-1,1,1-trifluoropropane.

2-trifluoromethyl acrylic acid cyclooctyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −65.9 (t, J=1.48 Hz)

GC-MS MS (CI): m/z 249 (M⁺−1)

Comparative Example 12

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), cyclooctanol (0.154 g, 1.2 mmol), triethylamine (0.223 g,2.2 mmol), dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01mmol), and toluene (2.0 mL), which were stirred at 120° C. for 5 hoursafter introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt to precipitate.,Quantification using a ¹⁹F—NMR integration value revealed that2-trifluoromethyl acrylic acid cyclooctyl ester was obtained with ayield of 72.3% on the basis of 2,3-dibromo-1,1,1-trifluoropropane. Also5.2% of 3-cyclohexyloxy-2-(trifluoromethyl)propionic acid cyclohexylester was obtained.

3-cyclooctyloxy-2-(trifluoromethyl)propionic acid cyclooctyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −66.7(d, J=8.52 Hz)

Example 16

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 1-cyclohexylethanol (0.154 g, 1.2 mmol), triethylamine(0.202 g, 2.0 mmol), sodium t-butoxide (0.0192 g, 0.2 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtoluene (2.0 mL), which were stirred at 120° C. for 5 hours afterintroducing carbon monoxide (1.0 MPaG). After the end of the reaction,the autoclave was cooled, ventilated, and added with benzotrifluoride asan internal standard substance, followed by stirring and leaving stillfor a while to let a salt precipitate. Quantification using a ¹⁹F—NMRintegration value revealed that 2-trifluoromethyl acrylic acid1-cyclohexylethyl ester was obtained with a yield of 75.0% on the basisof 2,3-dibromo-1,1,1-trifluoropropane.

2-trifluoromethyl acrylic acid 1-cyclohexylethyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −65.7 (t, J=1.37 Hz)

GC-MS MS (CI): m/z 249 (M⁺−1)

Comparative Example 13

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 1-cyclohexyl ethanol (0.154 g, 1.2 mmol), triethylamine(0.223 g, 2.2 mmol), dichlorobis(triphenylphosphine)palladium(II)(0.0070 g, 0.01 mmol), and toluene (2.0 mL), which were stirred at 120°C. for 5 hours after introducing carbon monoxide (1.0 MPaG). After theend of the reaction, the autoclave was cooled, ventilated, and addedwith benzotrifluoride as an internal standard substance, followed bystirring and leaving still for a while to let a salt precipitate.Quantification using a 19F—NMR integration value revealed that2-trifluoromethyl acrylic acid 1-cyclohexyl ethyl ester was obtainedwith a yield of 61.5% on the basis of2,3-dibromo-1,1,1-trifluoropropane. Also 5.9% of3-(1-cyclohexylethyloxy)-2-(trifluoromethyl)propionic acid1-cyclohexylethyl ester was obtained.

3-(1-cyclohexylethyloxy)-2-(trifluoromethyl)propionic acid1-cyclohexylethyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −66.55 (d, J=8.52 Hz), −66.62 (d,J=8.52 Hz), −66.63 (d, J=8.61 Hz), −66.68 (d, J=8.59 Hz)

Example 17

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 1-cyclohexyl ethanol (0.154 g, 1.2 mmol), triethylamine(0.202 g, 2.0 mmol), sodium carbonate (0.0106 g, 0.1 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtoluene (2.0 mL), which were then stirred at 100° C. for 15 hours afterintroducing carbon monoxide (1.0 MPaG). After the end of the reaction,the autoclave was cooled, ventilated, and added with benzotrifluoride asan internal standard substance, followed by stirring and leaving stillfor a while to let a salt precipitate. Quantification using a ¹⁹F—NMRintegration value revealed that 2-trifluoromethyl acrylic acid1-cyclohexylethyl ester was obtained with a yield of 74.2% on the basisof 2,3-dibromo-1,1,1-trifluoropropane. Also 1.9% of3-(1-cyclohexylethyloxy)-2-(trifluoromethyl)propionic acid1-cyclohexylethyl ester was obtained.

Example 18

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 1-menthol (0.188 g, 1.2 mmol), triethylamine (0.202 g, 2.0mmol), 60%-sodium hydride (0.0080 g, 0.2 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtoluene (2.0 mL), which were then stirred at 120° C. for 15 hours afterintroducing carbon monoxide (1.0 MPaG). After the end of the reaction,the autoclave was cooled, ventilated, and added with benzotrifluoride asan internal standard substance, followed by stirring and leaving stillfor a while to let a salt precipitate. Quantification using a ¹⁹F—NMRintegration value revealed that 2-trifluoromethyl acrylic acid 1-menthylester was obtained with a yield of 73.2% on the basis of2,3-dibromo-1,1,1-trifluoropropane. Also 1.0% of3-(1-menthyloxy)-2-(trifluoromethyl)propionic acid 1-menthyl ester wasobtained.

2-trifluoromethyl acrylic acid 1-menthyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −65.6 (t, J=1.48 Hz)

3-(1-menthyloxy)-2-(trifluoromethyl)propionic acid 1-menthyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −66.53 (d, J=8.53 Hz), −66.59 (d,J=8.58 Hz)

Comparative Example 14

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 1-menthol (0.188 g, 1.2 mmol), triethylamine (0.223 g, 2.2mmol), dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01mmol), and toluene (2.0 mL), which were then stirred at 120° C. for 15hours after introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid 1-menthyl ester was obtained with a yield of 43.1% on thebasis of 2,3-dibromo-1,1,1-trifluoropropane. Also 6.7% of3-(1-menthyloxy)-2-(trifluoromethyl)propionic acid 1-menthyl ester wasobtained.

Example 19

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 1-menthol (0.188 g, 1.2 mmol), triethylamine (0.202 g, 2.0mmol), sodium carbonate (0.0106 g, 0.1 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtetrahydrofuran (2.0 mL), which were then stirred at 100° C. for 5 hoursafter introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid 1-menthyl ester was obtained with a yield of 88.3% on thebasis of 2,3-dibromo-1,1,1-trifluoropropane.

Example 20

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 1-menthol (0.188 g, 1.2 mmol), triethylamine (0.202 g, 2.0mmol), lithium carbonate (0.0074 g, 0.1 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtetrahydrofuran (2.0 mL), which were then stirred at 100° C. for 5 hoursafter introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid 1-menthyl ester was obtained with a yield of 90.4% on thebasis of 2,3-dibromo-1,1,1-trifluoropropane.

Example 21

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), t-butyl alcohol (0.111 g, 1.5 mmol), triethylamine (0.202g, 2.0 mmol), sodium t-butoxide (0.0192 g, 0.2 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtoluene (2.0 mL), which were then stirred at 100° C. for 15 hours afterintroducing carbon monoxide (1.0 MPaG). After the end of the reaction,the autoclave was cooled, ventilated, and added with benzotrifluoride asan internal standard substance, followed by stirring and leaving stillfor a while to let a salt precipitate. Quantification using a ¹⁹F—NMRintegration value revealed that 2-trifluoromethyl acrylic acid t-butylester was obtained with a yield of 81.1% on the basis of2,3-dibromo-1,1,1-trifluoropropane.

2-trifluoromethyl acrylic acid t-butyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −65.8 (t, J=1.41 Hz)

GC-MS MS (CI): m/z 197 (M⁺+1)

Comparative Example 15

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), t-butyl alcohol (0.089 g, 1.2 mmol), triethylamine (0.223g, 2.2 mmol), dichlorobis(triphenylphosphine)palladium(II) (0.0070 g,0.01 mmol), and toluene (2.0 mL), which were then stirred at 100° C. for15 hours after introducing carbon monoxide (1.0 MPaG). After the end ofthe reaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid t-butyl ester was obtained with a yield of 24.8% on thebasis of 2,3-dibromo-1,1,1-trifluoropropane. Also 4.6% of3-(t-butyloxy)-2-(trifluoromethyl)propionic acid t-butyl ester wasobtained.

3-(t-butyloxy)-2-(trifluoromethyl)propionic acid t-butyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −66.9 (d, J=8.61 Hz)

Example 22

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), t-butyl alcohol (0.111 g, 1.5 mmol), triethylamine (0.202g, 2.0 mmol), sodium carbonate (0.0106 g, 0.1 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtetrahydrofuran (2.0 mL), which were then stirred at 100° C. for 5 hoursafter introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid t-butyl ester was obtained with a yield of 80.6% on thebasis of 2,3-dibromo-1,1,1-trifluoropropane.

Example 23

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), t-butyl alcohol (0.089 g, 1.2 mmol), triethylamine (0.202g, 2.0 mmol), lithium carbonate (0.0074 g, 0.1 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtetrahydrofuran (2.0 mL), which were then stirred at 100° C. for 5 hoursafter introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid t-butyl ester was obtained with a yield of 82.2% on thebasis of 2,3-dibromo-1,1,1-trifluoropropane.

Example 24

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), t-butyl alcohol (0.089 g, 1.2 mmol), triethylamine (0.202g, 2.0 mmol), lithium carbonate (0.0148 g, 0.2 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtetrahydrofuran (2.0 mL), which were then stirred at 100° C. for 5 hoursafter introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid t-butyl ester was obtained with a yield of 84.9% on thebasis of 2,3-dibromo-1,1,1-trifluoropropane.

Example 25

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), t-butyl alcohol (0.089 g, 1.2 mmol), triethylamine (0.202g, 2.0 mmol), lithium carbonate (0.0369 g, 0.5 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtetrahydrofuran (2.0 mL), which were then stirred at 100° C. for 5 hoursafter introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid t-butyl ester was obtained with a yield of 84.4% on thebasis of 2,3-dibromo-1,1,1-trifluoropropane.

Example 26

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 1-adamantanol (0.183 g, 1.2 mmol), triethylamine (0.202 g,2.0 mmol), 60%-sodium hydride (0.0080 g, 0.2 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtetrahydrofuran (2.0 mL), which were then stirred at 100° C. for 5 hoursafter introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid 1-admantyl ester was obtained with a yield of 87.9% on thebasis of 2,3-dibromo-1,1,1-trifluoropropane.

2-trifluoromethyl acrylic acid 1-admantyl ester

¹⁹F-NMR (250 MHz, CDCl₃, δ ppm): −65.5 (t, J=1.48 Hz)

Comparative Example 16

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 1-adamantanol (0.183 g, 1.2 mmol), triethylamine (0.223 g,2.2 mmol), dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01mmol), and tetrahydrofuran (2.0 mL), which were then stirred at 100° C.for 15 hours after introducing carbon monoxide (1.0 MPaG). After the endof the reaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid 1-admantyl ester was obtained with a yield of 23.7% on thebasis of 2,3-dibromo-1,1,1-trifluoropropane. Also, 0.6% of3-(1-adamantyloxy)-2-(trifluoromethyl)propionic acid 1-admantyl esterwas obtained.

3-(1-adamantyloxy)-2-(trifluoromethyl)propionic acid 1-admantyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −66.6 (d, J=8.60 Hz)

Example 27

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 1-adamantanol (0.183 g, 1.2 mmol), triethylamine (0.202 g,2.0 mmol), lithium carbonate (0.0074 g, 0.1 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtetrahydrofuran (2.0 mL), which were then stirred at 100° C. for 5 hoursafter introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid 1-admantyl ester was obtained with a yield of 89.0% on thebasis of 2,3-dibromo-1,1,1-trifluoropropane.

Example 28

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 2-methyl-2-adamantanol (0.249 g, 1.5 mmol), triethylamine(0.202 g, 2.0 mmol), sodium carbonate (0.0106 g, 0.1 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtetrahydrofuran (2.0 mL), which were then stirred at 100° C. for 5 hoursafter introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid 2-methyl-2-adamantyl ester was obtained with a yield of70.5% on the basis of 2,3-dibromo-1,1,1-trifluoropropane.

2-trifluoromethyl acrylic acid 2-methyl-2-adamantyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −65.5 (t, J=1.53 Hz)

Comparative Example 17

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 2-methyl-2-adamantanol (0.332 g, 2.0 mmol), triethylamine(0.223 g, 2.2 mmol), dichlorobis(triphenylphosphine)palladium(II)(0.0070 g, 0.01 mmol), and tetrahydrofuran (2.0 mL), which were thenstirred at 120° C. for 15 hours after introducing carbon monoxide (1.0MPaG). After the end of the reaction, the autoclave was cooled,ventilated, and added with benzotrifluoride as an internal standardsubstance, followed by stirring and leaving still for a while to let asalt precipitate. Quantification using a ¹⁹F—NMR integration valuerevealed that 2-trifluoromethyl acrylic acid 2-methyl-2-adamantyl esterwas obtained with a yield of 19.1% on the basis of2,3-dibromo-1,1,1-trifluoropropane.

Example 29

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 2-methyl-2-adamantanol (0.249 g, 1.5 mmol), triethylamine(0.202 g, 2.0 mmol), lithium carbonate (0.0369 g, 0.5 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtetrahydrofuran (2.0 mL), which were then stirred at 100° C. for 15hours after introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid 2-methyl-2-adamantyl ester was obtained with a yield of91.1% on the basis of 2,3-dibromo-1,1,1-trifluoropropane.

Example 30

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 2-butyl-2-adamantanol (0.313 g, 1.5 mmol), triethylamine(0.202 g, 2.0 mmol), sodium carbonate (0.0106 g, 0.1 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtetrahydrofuran (2.0 mL), which were then stirred at 100° C. for 15hours after introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid 2-butyl-2-adamantyl ester was obtained with a yield of41.9% on the basis of 2,3-dibromo-1,1,1-trifluoropropane.

2-trifluoromethyl acrylic acid 2-butyl-2-adamantyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −65.6 (t, J=1.45 Hz)

Example 31

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 2-butyl-2-adamantanol (0.313 g, 1.5 mmol), triethylamine(0.202 g, 2.0 mmol), lithium carbonate (0.0369 g, 0.5 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andcyclopentylmethyl ether (2.0 mL), which were then stirred at 100° C. for15 hours after introducing carbon monoxide (1.0 MPaG). After the end ofthe reaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F-NMR integration value revealed that 2-trifluoromethylacrylic acid 2-butyl-2-adamantyl ester was obtained with a yield of74.5% on the basis of 2,3-dibromo-1,1,1-trifluoropropane.

Example 32

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 1,3-adamantane diol (0.202 g, 1.2 mmol), triethylamine(0.202 g, 2.0 mmol), 60%-sodium hydride (0.0080 g, 0.2 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtetrahydrofuran (2.0 mL), which were then stirred at 100° C. for 15hours after introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that mono(2-trifluoromethyl)acrylic acid 1,3-adamantanediyl ester was obtained with a yield of 62.8%on the basis of 2,3-dibromo-1,1,1-trifluoropropane. Also 21.7% (0.108mmol) of bis(2-trifluoromethyl) acrylic acid 1,3-adamantanediyl esterwas obtained.

Mono(2-trifluoromethyl) acrylic acid 1,3-adamantadiyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −65.81 (t, J=1.50 Hz)

bis(2-trifluoromethyl) acrylic acid 1,3-adamantadiyl ester

¹⁹F—NMR (250 MHz, CDCl₃, δ ppm): −65.80 (t, J=1.48 Hz)

Comparative Example 18

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 1,3-adamantane diol (0.168 g, 1.0 mmol), triethylamine(0.223 g, 2.2 mmol), dichlorobis(triphenylphosphine)palladium(II)(0.0070 g, 0.01 mmol), and tetrahydrofuran (2.0 mL), which were thenstirred at 100° C. for 15 hours after introducing carbon monoxide (1.0MPaG). After the end of the reaction, the autoclave was cooled,ventilated, and added with benzotrifluoride as an internal standardsubstance, followed by stirring and leaving still for a while to let asalt precipitate. Quantification using a ¹⁹F—NMR integration valuerevealed that mono(2-trifluoromethyl) acrylic acid 1,3-adamantanediylester was obtained with a yield of 18.7% on the basis of2,3-dibromo-1,1,1-trifluoropropane. Also 7.3% (0.036 mmol) ofbis(2-trifluoromethyl) acrylic acid 1,3-adamantanediyl ester wasobtained.

Example 33

An autoclave was charged with 2,3-dibromo-1,1,1-trifluoropropane (0.2559g, 1.0 mmol), 1,3-adamantane diol (0.202 g, 1.2 mmol), triethylamine(0.202 g, 2.0 mmol), sodium carbonate (0.0106 g, 0.1 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtetrahydrofuran (2.0 mL), which were then stirred at 100° C. for 15hours after introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that mono(2-trifluoromethyl)acrylic acid 1,3-adamantanediyl ester was obtained with a yield of 67.1%on the basis of 2,3-dibromo-1,1,1-trifluoropropane. Also 20.4% (0.102mmol) of bis(2-trifluoromethyl) acrylic acid 1,3-adamantanediyl esterwas obtained.

Example 34

An autoclave was charged with 2-bromo-3,3,3-trifluoropropene (0.175 g,1.0 mmol), ethanol (0.055 g, 1.2 mmol), triethylamine (0.101 g, 1.0mmol), lithium carbonate (0.0074 g, 0.1 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtetrahydrofuran (2.0 mL), which were then stirred at 100° C. for 5 hoursafter introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid ethyl ester was obtained with a yield of 82.0% on the basisof 2-bromo-3,3,3-trifluoropropene. Also 3.3% of3-ethoxy-2-(trifluoromethyl)propionic acid ethyl ester was obtained.

Comparative Example 19

An autoclave was charged with 2-bromo-3,3,3-trifluoropropene (0.175 g,1.0 mmol), ethanol (0.055 g, 1.2 mmol), triethylamine (0.111 g, 1.1mmol), dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01mmol), and tetrahydrofuran (2.0 mL), which were then stirred at 100° C.for 5 hours after introducing carbon monoxide (1.0 MPaG). After the endof the reaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid ethyl ester was obtained with a yield of 62.1% on the basisof 2-bromo-3,3,3-trifluoropropene. Also 16.7% of3-ethoxy-2-(trifluoromethyl)propionic acid ethyl ester was obtained.

Example 35

An autoclave was charged with 2-bromo-3,3,3-trifluoropropene (0.175 g,1.0 mmol), t-butyl alcohol (0.089 g, 1.2 mmol), triethylamine (0.101 g,1.0 mmol), lithium carbonate (0.0148 g, 0.2 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtetrahydrofuran (2.0 mL), which were then stirred at 100° C. for 5 hoursafter introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid t-butyl ester was obtained with a yield of 75.7% on thebasis of 2-bromo-3,3,3-trifluoropropene.

Comparative Example 20

An autoclave was charged with 2-bromo-3,3,3-trifluoropropene (0.175 g,1.0 mmol), t-butyl alcohol (0.089 g, 1.2 mmol), triethylamine (0.111 g,1.1 mmol), dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01mmol), and tetrahydrofuran (2.0 mL), which were then stirred at 100° C.for 5 hours after introducing carbon monoxide (1.0 MPaG). After the endof the reaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid t-butyl ester was obtained with a yield of 12.6% on thebasis of 2-bromo-3,3,3-trifluoropropene.

Example 36

An autoclave was charged with 2-bromo-3,3,3-trifluoropropene (0.175 g,1.0 mmol), 1-adamantanol (0.183 g, 1.2 mmol), triethylamine (0.101 g,1.0 mmol), lithium carbonate (0.0074 g, 0.1 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtetrahydrofuran (2.0 mL), which were then stirred at 100° C. for 15hours after introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid 1-admantyl ester was obtained with a yield of 80.2% on thebasis of 2-bromo-3,3,3-trifluoropropene.

Comparative Example 21

An autoclave was charged with 2-bromo-3,3,3-trifluoropropene (0.175 g,1.0 mmol), 1-adamantanol (0.183 g, 1.2 mmol), triethylamine (0.111 g,1.1 mmol), dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01mmol), and tetrahydrofuran (2.0 mL), which were then stirred at 100° C.for 15 hours after introducing carbon monoxide (1.0 MPaG). After the endof the reaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid 2-adamantyl ester was obtained with a yield of 13.9% on thebasis of 1-bromo-3,3,3-trifluoropropene.

Example 37

An autoclave was charged with 2-bromo-3,3,3-trifluoropropene (0.175 g,1.0 mmol), 2-methyl-2-adamantanol (0.200 g, 1.2 mmol), triethylamine(0.101 g, 1.0 mmol), lithium carbonate (0.0369 g, 0.5 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andtetrahydrofuran (2.0 mL), which were then stirred at 100° C. for 15hours after introducing carbon monoxide (1.0 MPaG). After the end of thereaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F—NMR integration value revealed that 2-trifluoromethylacrylic acid 2-methyl-2-adamantyl ester was obtained with a yield of79.6% on the basis of 2-bromo-3,3,3-trifluoropropene.

Comparative Example 22

An autoclave was charged with 2-bromo-3,3,3-trifluoropropene (0.175 g,1.0 mmol), 2-methyl-2-adamantanol (0.200 g, 1.2 mmol), triethylamine(0.111 g, 1.1 mmol), dichlorobis(triphenylphosphine)palladium(II)(0.0070 g, 0.01 mmol), and tetrahydrofuran (2.0 mL), which were thenstirred at 100° C. for 15 hours after introducing carbon monoxide (1.0MPaG). After the end of the reaction, the autoclave was cooled,ventilated, and added with benzotrifluoride as an internal standardsubstance, followed by stirring and leaving still for a while to let asalt precipitate. Quantification using a ¹⁹F—NMR integration valuerevealed that 2-trifluoromethyl acrylic acid 2-methyl-2-adamantyl esterwas obtained with a yield of 4.1% on the basis of2-bromo-3,3,3-trifluoropropene.

Example 38

An autoclave was charged with 2-bromo-3,3,3-trifluoropropene (0.175 g,1.0 mmol), 2-butyl-2-adamantanol (0.250 g, 1.2 mmol), triethylamine(0.101 g, 1.0 mmol), lithium carbonate (0.0148 g, 0.2 mmol),dichlorobis(triphenylphosphine)palladium(II) (0.0070 g, 0.01 mmol), andcyclopentylmethyl ether (2.0 mL), which were then stirred at 100° C. for15 hours after introducing carbon monoxide (1.0 MPaG). After the end ofthe reaction, the autoclave was cooled, ventilated, and added withbenzotrifluoride as an internal standard substance, followed by stirringand leaving still for a while to let a salt precipitate. Quantificationusing a ¹⁹F-NMR integration value revealed that 2-trifluoromethylacrylic acid 2-butyl-2-adamantyl ester was obtained with a yield of70.1% on the basis of 2-bromo-3,3,3-trifluoropropene.

Comparative Example 23

An autoclave was charged with 2-bromo-3,3,3-trifluoropropene (0.175 g,1.0 mmol), 2-butyl-2-adamantanol (0.250 g, 1.2 mmol), triethylamine(0.111 g, 1.1 mmol), dichlorobis(triphenylphosphine)palladium(II)(0.0070 g, 0.01 mmol), and cyclopentylmethyl ether (2.0 mL), which werethen stirred at 100° C. for 15 hours after introducing carbon monoxide(1.0 MPaG). After the end of the reaction, the autoclave was cooled,ventilated, and added with benzotrifluoride as an internal standardsubstance, followed by stirring and leaving still for a while to let asalt precipitate. Quantification using a ¹⁹F—NMR integration valuerevealed that 2-trifluoromethyl acrylic acid 2-butyl-2-adamantyl esterwas obtained with a yield of 4.2% on the basis of2-bromo-3,3,3-trifluoropropene.

INDUSTRIAL APPLICABILITY

The present invention provides a simple and highly versatile andselective process for producing a fluorine-containing acrylic acid esterwhich is a useful compound having wide applications in materials forpharmaceuticals and functional polymers.

1. A process for producing a fluorine-containing acrylic acid esterrepresented by the general formula (IV):

(wherein, Rf represents a perfluoroalkyl group and R represents anunsubstituted or substituted alkyl group), which comprises reacting1-bromo-1-perfluoroalkylethene represented by the general formula (I):

(wherein Rf is as defined above), or 1,2-dibromo-1-perfluoroalkylethanerepresented by the general formula (II):

(wherein Rf is as defined above) with an alcohol represented by thegeneral formula (III):ROH  (III) (wherein R is as defined above) in the presence of apalladium catalyst, carbon monoxide, and two or more bases, wherein atleast one of the bases is an inorganic base, an inorganic salt, or anorganic metal, and at least one of the bases is an amine.
 2. The processaccording to claim 1, wherein the inorganic base, the inorganic salt, orthe organic metal is used in a molar ratio of 0.001 to 1, relative tothe compound represented by the general formula (I) or (II).
 3. Theprocess according to claim 1, wherein the alcohol is a straight,branched, or cyclic aliphatic alcohol.
 4. The process according to claim1, wherein the amine is used in a molar ratio of at least 1, relative tothe compound represented by the general formula (I) or (II).
 5. Theprocess according to claim 2, wherein the alcohol is a straight,branched, or cyclic aliphatic alcohol.